CN101712756A - Sulfonated polyether and phosphine oxide and preparation method thereof - Google Patents
Sulfonated polyether and phosphine oxide and preparation method thereof Download PDFInfo
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- CN101712756A CN101712756A CN200910228681A CN200910228681A CN101712756A CN 101712756 A CN101712756 A CN 101712756A CN 200910228681 A CN200910228681 A CN 200910228681A CN 200910228681 A CN200910228681 A CN 200910228681A CN 101712756 A CN101712756 A CN 101712756A
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- sulfonated polyether
- sulfonation degree
- oxidation thing
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Abstract
The invention discloses a sulfonated copolymer, all main chains of which have the ether and phosphine oxide structure. The sulfonated copolymer comprises a random sulfonated polyether and phosphine oxide copolymer and an alternative sulfonated polyether and phosphine oxide copolymer. Meanwhile, the invention also discloses application of the sulfonated polyether and phosphine oxide in the field of water treatment by a membrane method and the aspect of proton exchange membrane fuel cells.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to poly aromatic ether phosphine oxide family macromolecule polymkeric substance and preparation method thereof.
Background technology
The phosphine oxide structural unit, chemical property is stable, and is high temperature resistant, has a wide range of applications in fire-retardant material.The macromolecular material that contains sulfonic acid group and phosphine oxide structure in the embrane method water treatment, comprises reverse osmosis, nanofiltration, ultrafiltration, micro-filtration etc., and the Proton Exchange Membrane Fuel Cells field, and wide application prospect is all arranged.Wherein sulfonated polyether sulfone phosphine oxide macromolecular material is compared with sulfonated polyether sulfone, under identical loading capacity, has higher desalination rate and permeable amount.Simultaneously, the former also has higher mechanical properties.In addition, sulfonated polyether sulfone phosphine oxide macromolecular material has proton conductivity preferably.Generally believe that keying action has been played in the raising of stronger interaction partners material property between the phosphono group.This class material can pass through sulfonated monomers, for example 3,3 '-sodium disulfonate-4,4 '-dichloro diphenyl sulfone, 3,3 '-sodium disulfonate-4,4 '-difluorodiphenyl sulfone, two (4-fluorophenyls) (3-sodium sulfonate phenyl) phosphine oxide, with the activatory aromatic dihalide and the diphenol that do not contain sulfonic acid group, make through fragrant nucleophilic substitution reaction copolymerization, for example:
Random sulfonated polyether sulfone phosphine oxide (sulfonation group is positioned on the sulfone monomer)
Random sulfonated polyether sulfone phosphine oxide (sulfonation group is positioned on the phosphine oxide monomer)
The main chain that contains sulfonic acid group all is that the macromolecular material of phosphine oxide-ether structure there is no report.The content of phosphono group will further improve in this class material, thereby may bring it to handle the improved performance of material and proton exchange membrane material as film water.Simultaneously, ionic group shared mass ratio in phosphine oxide monomer is less, therefore, even only adopt sulfonated monomers and diphenol polymerization (not to add non-sulfonated monomers, sulfonation degree 100%), the loading capacity of the macromolecular material that obtains can be not too high yet, and its mechanical property still might be maintained.This kind method will provide sulfonated polyether and phosphine oxide alternating copolymer macromolecular material.These materials all do not have report.
Summary of the invention
The invention provides the main chain that contains sulfonic acid group all is the macromolecular material of phosphine oxide-ether structure.Adopt the polyreaction of two (4-fluorophenyl) phenylphosphine oxide, two (4-fluorophenyl) methylphosphine oxide compound, two (4-hydroxy phenyl) phenylphosphine oxide and two (4-fluorophenyl) (3-sodium sulfonate phenyl) phosphine oxides, the polyether and phosphine oxide polymer series that contains different ratios ionic group material is provided.Comprise random and the alternative sulfonated polyether and phosphine oxide.For achieving the above object, technical scheme provided by the invention is as follows:
Sulfonated polyether and phosphine oxide with following structural formula comprises alternately and random copolymers:
R=C1-4 alkyl or phenyl wherein; R1, the R2=C1-4 alkyl or phenyl, but inequality; M=lithium, sodium, potassium, caesium and ammonium ion; N=5-200; A+b=1, a, b＞0, m=5-200; C+d+e=1, c, d, e＞0, q=5-200.Sulfonated polyether and phosphine oxide of the present invention, wherein the multipolymer of representative is as follows:
(1) random sulfonated polyether triphenylphosphine oxidation thing (10% sulfonation degree, sylvite)
(2) random sulfonated polyether triphenylphosphine oxidation thing (20% sulfonation degree, sylvite)
(3) random sulfonated polyether triphenylphosphine oxidation thing (30% sulfonation degree, sylvite)
(4) random sulfonated polyether triphenylphosphine oxidation thing (40% sulfonation degree, sylvite)
(5) random sulfonated polyether triphenylphosphine oxidation thing (50% sulfonation degree, sylvite)
(6) random sulfonated polyether triphenylphosphine oxidation thing (60% sulfonation degree, sylvite)
(7) random sulfonated polyether triphenylphosphine oxidation thing (70% sulfonation degree, sylvite)
(8) random sulfonated polyether triphenylphosphine oxidation thing (80% sulfonation degree, sylvite)
(9) random sulfonated polyether triphenylphosphine oxidation thing (90% sulfonation degree, sylvite)
(10) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, sylvite)
(11) random sulfonated polyether methyldiphenyl base phosphine oxide (50% sulfonation degree, sylvite)
(12) random sulfonated polyether triphenylphosphine oxidation thing (50% sulfonation degree, sulfonic acid)
(13) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, sulfonic acid)
(14) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, lithium salts)
(15) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, sodium salt)
(16) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, cesium salt)
(17) replace sulfonated polyether triphenylphosphine oxidation thing (100% sulfonation degree, ammonium salt)
(18) random sulfonated polyether methyldiphenyl base phosphine oxide-polyethers triphenylphosphine oxidation thing (50% sulfonation degree, sylvite)
The high molecular preparation method of sulfonated polyether and phosphine oxide of the present invention:
The monomer structure molfraction
By certain feed ratio, A-D is various monomeric molfractions, in the presence of carbonate, in high boiling aprotic polar solvent, in the presence of the azeotropic dehydration solvent, heat the certain hour that dewaters earlier at a certain temperature, boil off dehydrated solvent, be elevated to certain temperature again and continue the reaction certain hour, obtain corresponding macromolecular compound, wherein: 0≤A, B＜1,0＜C≤1, and A+B+C=D=1.R=C1-4 alkyl or phenyl wherein; R
1, R
2=C1-4 alkyl or phenyl, but inequality; M=lithium, sodium, potassium, caesium and ammonium ion; N=5-200; A+b=1, a, b＞0, m=5-200; C+d+e=1, c, d, e＞0, q=5-200.
Described preparation method of the present invention, wherein in the presence of carbonate, in high boiling aprotic polar solvent, in the presence of the azeotropic dehydration solvent, under 140-160 ℃ of temperature, heat earlier and dewatered 4-12 hour, boil off dehydrated solvent, be elevated to 160-195 ℃ again and continue reaction 12-48 hour, after reaction mixture is cooled to room temperature, be poured in the deionized water, obtain the white fiber shaped polymer, under 60-80 ℃ of condition, soaked 5-10 hour then, repeat 3-5 time, filter, oven dry, vacuum-drying obtains corresponding polyether and phosphine oxide family macromolecule compound.
Described preparation method of the present invention, wherein said carbonate is Na
2CO
3, K
2CO
3Or Cs
2CO
3
Described preparation method of the present invention, wherein said high boiling point non-protonic solvent is N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or N-Methyl pyrrolidone.
Described preparation method of the present invention, wherein said dehydrated solvent is hexanaphthene, toluene, dimethylbenzene or chlorobenzene.
Described preparation method of the present invention, the volume of wherein said dehydrated solvent is 1/2 to 1/1 of a reaction solvent volume.
Described sulfonated polyether and phosphine oxide of the present invention is in embrane method water treatment field such as reverse osmosis, nanofiltration, ultrafiltration, micro-filtrations, and the application of Proton Exchange Membrane Fuel Cells aspect.
The volume ratio of all monomeric quality of dissolved and the non-proton property of high boiling point reaction solvent is 15% to 65% in the reaction mixture described in the preparation method of the present invention, but is the best with 20%.
Dehydration temperaturre described in the preparation method of the present invention is 140-160 ℃, is the best with 160 ℃.
The dehydration reaction time described in the preparation method of the present invention is 4-12 hour, is the best with 6 hours.
Temperature of reaction 160-195 described in the preparation method of the present invention ℃ is the best with 185 ℃.
Reaction times described in the preparation method of the present invention is 12-48 hour, is the best with 24 hours.
The experimental installation that the present invention adopts as shown in Figure 2, by reflux condensing tube 1, bubbler 2, water trap 3, mechanical stirring 4, water trap piston 5, oil bath device 6 grades connect and compose.
The viscosity test condition that the present invention adopts: the intrinsic viscosity of sulfonated polyether and phosphine oxide macromolecular material adopts the Ubbelohde viscosimetry to measure, and probe temperature is 25 ℃, and solvent is the nmp solution that contains the 0.05M lithiumbromide.
The title of partial monosomy used in the present invention, structure and code name are as shown in table 1.
Description of drawings
(the R=C1-4 alkyl or phenyl wherein of the structural formula of the polymkeric substance of indication among Fig. 1 the present invention; R
1, R
2=C1-4 alkyl or phenyl, but inequality; M=lithium, sodium, potassium, caesium and ammonium ion; A+b=1, a, b＞0; C+d+e=1, c, d, e＞0).
Fig. 2 the present invention adopts the preparation facilities sketch (wherein 1 reflux condensing tube, 2 bubblers, 3 water traps, 4 mechanical stirring, 5 water trap pistons, 6 oil bath devices, 7 nitrogen) of sulfonated poly aromatic ether.
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.The present invention is described further below in conjunction with comparative example.(R=C1-4 alkyl or phenyl wherein; R
1, R
2=C1-4 alkyl or phenyl, but inequality; M=lithium, sodium, potassium, caesium and ammonium ion; A+b=1, a, b＞0; C+d+e=1, c, d, e＞0), wherein used monomer all has commercially available.
The title of partial monosomy used in the present invention, structure and code name.
Table 1
Two (4-fluorophenyl) phenylphosphine oxide
BFPPO
Two (4-fluorophenyl) methylphosphine oxide compound
BFMPO
Two (4-fluorophenyls) (3-sodium sulfonate phenyl) phosphine oxide
SBFPPO
Two (4-hydroxy phenyl) phenylphosphine oxide
BOHPPO
Embodiment 1:
By reaction unit shown in Figure 2, with BFPPO (28.2843g, 90mmol), SBFPPO (4.1631g, 10mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 317mL N, N-N,N-DIMETHYLACETAMIDE, 159mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 54.5g again, yield: 97%, intrinsic viscosity: 0.88dL/g.
Embodiment 2:
By reaction unit shown in Figure 2, with BFPPO (25.1416g, 80mmol), SBFPPO (8.3262g, 20mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 322mL N, N-N,N-DIMETHYLACETAMIDE, 161mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 54.9g again, yield: 96%, intrinsic viscosity: 0.80dL/g.
Embodiment 3:
By reaction unit shown in Figure 2, with BFPPO (21.9989g, 70mmol), SBFPPO (12.4893g, 30mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 327mL N, N-N,N-DIMETHYLACETAMIDE, 164mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 56.5g again, yield: 97%, intrinsic viscosity: 0.75dL/g.
Embodiment 4:
By reaction unit shown in Figure 2, with BFPPO (18.8562g, 60mmol), SBFPPO (16.6524g, 40mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 333mL N, N-N,N-DIMETHYLACETAMIDE, 167mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 56.3g again, yield: 95%, intrinsic viscosity: 0.68dL/g.
Embodiment 5:
By reaction unit shown in Figure 2, with BFPPO (15.7135g, 50mmol), SBFPPO (20.8155g, 50mmol), BOH PPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 338mL N, N-N,N-DIMETHYLACETAMIDE, 169mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 56.6g again, yield: 94%, intrinsic viscosity: 0.62dL/g.
Embodiment 6:
By reaction unit shown in Figure 2, with BFPPO (12.5708g, 40mmol), SBFPPO (24.9786g, 60mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 343mL N, N-N,N-DIMETHYLACETAMIDE, 172mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 57.6g again, yield: 94%, intrinsic viscosity: 0.59dL/g.
Embodiment 7:
By reaction unit shown in Figure 2, with BFPPO (9.4281g, 30mmol), SBFPPO (29.1417g, 70mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 348mL N, N-N,N-DIMETHYLACETAMIDE, 174mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 59.2g again, yield: 95%, intrinsic viscosity: 0.55dL/g.
Embodiment 8:
By reaction unit shown in Figure 2, with BFPPO (6.2854g, 20mmol), SBFPPO (33.3048g, 80mmol), BOH PPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 353mL N, N-N,N-DIMETHYLACETAMIDE, 177mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 58.3g again, yield: 92%, intrinsic viscosity: 0.51dL/g.
Embodiment 9:
By reaction unit shown in Figure 2, with BFPPO (3.1427g, 10mmol), SBFPPO (37.4679g, 90mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 358mL N, N-N,N-DIMETHYLACETAMIDE, 179mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 59.8g again, yield: 93%, intrinsic viscosity: 0.48dL/g.
Embodiment 10:
By reaction unit shown in Figure 2, with SBFPPO (41.6310g, 100mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), the 363mL N,N-dimethylacetamide, 182mL toluene mixes, in 160 ℃ of branch water 6 hours, temperature of reaction rose to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (alternately sulfonated polyether and phosphine oxide polymer), 59.5g again, yield: 91%, intrinsic viscosity: 0.43dL/g.
Embodiment 11:
By reaction unit shown in Figure 2, with SBFPPO (20.8155g, 50mmol), BFMPO (12.6100g, 50mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), 322mL N, N-N,N-DIMETHYLACETAMIDE, 161mL toluene mixed, in 160 ℃ of branch water 6 hours, temperature of reaction rises to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 55.4g again, yield: 97%, intrinsic viscosity: 0.73dL/g.
Embodiment 12:
Obtain macromolecular material among the embodiment 5 and place 0.5MH2SO4, ebuillition of heated also kept 2 hours, place deionized water again, kept 8 hours in 80 ℃, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain tawny fibrous polymer (the random sulfonated polyether and phosphine oxide polymer of sour form) again.
Embodiment 13:
With the method for embodiment 12, obtain the alternately sulfonated polyether and phosphine oxide polymer of the sour form of embodiment 10.
Embodiment 14-17:
The sulfonated polyether and phosphine oxide polymer of the sour form that embodiment 13 is obtained places 1MLi respectively
2CO
3, Na
2CO
3, Cs
2CO
3, Et
3In the aqueous solution of N, ebuillition of heated also kept 2 hours, placed deionized water again, and in 80 ℃ of maintenances 8 hours, triplicate filtered, and oven dry 100 ℃ of following vacuum-dryings 24 hours, obtains lithium, sodium, caesium respectively again.The alternately sulfonated polyether and phosphine oxide polymer of ammonium salts.
Embodiment 18:
By reaction unit shown in Figure 2, with SBFPPO (20.8155g, 50mmol), BFPPO (7.8568g, 25mmol), BFMPO (6.3050g, 25mmol), BOHPPO (31.0280g, 100mmol), Anhydrous potassium carbonate (15.8942g, 115mmol), the 330mL N,N-dimethylacetamide, 165mL toluene mixes, in 160 ℃ of branch water 6 hours, temperature of reaction rose to 185 ℃, reacts 24 hours.Stop heating and stirring, naturally cool to room temperature.In the slow impouring 2L of the reaction solution deionized water, obtain the white fiber shaped polymer, soaked 8 hours under 80 ℃ of conditions with the 4L deionized water, triplicate filters, oven dry, 100 ℃ of following vacuum-dryings 24 hours, obtain light yellow fibrous polymer (random sulfonated polyether and phosphine oxide polymer), 56.4g again, yield: 96%, intrinsic viscosity: 0.70dL/g.
Embodiment 19:
The macromolecular material 500mg that embodiment 7 obtains after the dissolving of adding 10mL N,N-dimethylacetamide, filters through 0.45 μ m aperture strainer, places on 10 * 10cm sheet glass, through the infrared lamp heating, again through vacuum-drying, obtains flat sheet membrane.Under 400psi, the 2000ppmNaCl aqueous solution, the 25 ℃ of conditions, desalination rate 99.5%, coefficient of permeability 0.25L μ mm-2h-1bar-1.
Embodiment 20:
The macromolecular material 750mg that embodiment 7 obtains after the dissolving of adding 10mL N,N-dimethylacetamide, filters through 0.45 μ m aperture strainer, places on 10 * 10cm sheet glass, through the infrared lamp heating, again through vacuum-drying, obtains flat sheet membrane.Measuring proton conductivity in 30 ℃, water is 92mScm
-1
After the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the present invention also is not subjected to the restriction of the embodiment that gives an actual example in the specification sheets.
Claims (9)
1. the sulfonated polyether and phosphine oxide that has following structural formula comprises alternately and random copolymers:
R=C1-4 alkyl or phenyl wherein; R
1, R
2=C1-4 alkyl or phenyl, but inequality; M=lithium, sodium, potassium, caesium and ammonium ion; N=5-200; A+b=1, a, b＞0, m=5-200; C+d+e=1, c, d, e＞0, q=5-200.
2. the described sulfonated polyether and phosphine oxide of claim 1, wherein the multipolymer of representative is as follows:
(1) random sulfonated polyether triphenylphosphine oxidation thing, 10% sulfonation degree, sylvite
(2) random sulfonated polyether triphenylphosphine oxidation thing, 20% sulfonation degree, sylvite
(3) random sulfonated polyether triphenylphosphine oxidation thing, 30% sulfonation degree, sylvite
(4) random sulfonated polyether triphenylphosphine oxidation thing, 40% sulfonation degree, sylvite
(5) random sulfonated polyether triphenylphosphine oxidation thing, 50% sulfonation degree, sylvite
(6) random sulfonated polyether triphenylphosphine oxidation thing, 60% sulfonation degree, sylvite
(7) random sulfonated polyether triphenylphosphine oxidation thing, 70% sulfonation degree, sylvite
(8) random sulfonated polyether triphenylphosphine oxidation thing, 80% sulfonation degree, sylvite
(9) random sulfonated polyether triphenylphosphine oxidation thing, 90% sulfonation degree, sylvite
(10) replace sulfonated polyether triphenylphosphine oxidation thing 100% sulfonation degree, sylvite
(11) random sulfonated polyether methyldiphenyl base phosphine oxide, 50% sulfonation degree, sylvite
(12) random sulfonated polyether triphenylphosphine oxidation thing, 50% sulfonation degree, sulfonic acid
(13) replace sulfonated polyether triphenylphosphine oxidation thing, 100% sulfonation degree, sulfonic acid
(14) replace sulfonated polyether triphenylphosphine oxidation thing, 100% sulfonation degree, lithium salts
(15) replace sulfonated polyether triphenylphosphine oxidation thing, 100% sulfonation degree, sodium salt
(16) replace sulfonated polyether triphenylphosphine oxidation thing, 100% sulfonation degree, cesium salt
(17) replace sulfonated polyether triphenylphosphine oxidation thing, 100% sulfonation degree, ammonium salt
(18) random sulfonated polyether methyldiphenyl base phosphine oxide-polyethers triphenylphosphine oxidation thing 50% sulfonation degree, sylvite
3. the high molecular preparation method of the described sulfonated polyether and phosphine oxide of claim 1:
The monomer structure molfraction
A-D is various monomeric molfractions, by certain feed ratio, in the presence of carbonate, in high boiling aprotic polar solvent, in the presence of the azeotropic dehydration solvent, heat the certain hour that dewaters earlier at a certain temperature, boil off dehydrated solvent, be elevated to certain temperature again and continue the reaction certain hour, obtain corresponding macromolecular compound, wherein: 0≤A, B＜1,0＜C≤1, and A+B+C=D=1.
4. the described preparation method of claim 3, wherein in the presence of carbonate, in high boiling aprotic polar solvent, in the presence of the azeotropic dehydration solvent, under 140-160 ℃ of temperature, heat earlier and dewatered 4-12 hour, boil off dehydrated solvent, be elevated to 160-195 ℃ again and continue reaction 12-48 hour, after reaction mixture is cooled to room temperature, be poured in the deionized water, obtain the white fiber shaped polymer, under 60-80 ℃ of condition, soaked 5-10 hour then, repeat 3-5 time, filter, oven dry, vacuum-drying obtains corresponding polyether and phosphine oxide family macromolecule multipolymer.
5. the described preparation method of claim 3, wherein said carbonate is Na
2CO
3, K
2CO
3Or Cs
2CO
3
6. the described preparation method of claim 3, wherein said high boiling point non-protonic solvent is N, dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or N-Methyl pyrrolidone.
7. the described preparation method of claim 3, wherein said dehydrated solvent is hexanaphthene, toluene, dimethylbenzene or chlorobenzene.
8. the described preparation method of claim 3, the volume of wherein said dehydrated solvent is 1/2 to 1/1 of a reaction solvent volume.
9. the described sulfonated polyether and phosphine oxide of claim 1 is in embrane method water treatment field such as reverse osmosis, nanofiltration, ultrafiltration, micro-filtrations, and the application of Proton Exchange Membrane Fuel Cells aspect.
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| CN103073587A (en) * | 2013-01-11 | 2013-05-01 | 天津师范大学 | 3-sulfonic group-4-halophenyl-3'-sulfophenyl-4''-halophenylphosphine oxide and preparation method of salt thereof |
| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
| CN103897179A (en) * | 2014-04-01 | 2014-07-02 | 天津师范大学 | Efficient preparation method of polymers containing phosphonic acid groups and salts |
| CN104292453A (en) * | 2014-09-09 | 2015-01-21 | 天津师范大学 | Multi-sulfonated polyaromatic ether phosphine oxide high-molecular materials and preparation method and application thereof |
| CN105017751A (en) * | 2015-07-06 | 2015-11-04 | 天津师范大学 | Polymer blend with skeleton containing phosphonate acid and sulfonic acid group and preparation method for polymer blend |
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| CN100336845C (en) * | 2005-01-13 | 2007-09-12 | 上海交通大学 | Sulfonated aryl sulfoether containing triphenyl phosphinyl structure unit and its preparation method |
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| CN101445601A (en) * | 2008-12-18 | 2009-06-03 | 上海交通大学 | Sulfonated polyarylether based on triphenylphosphine oxide structure unit and preparation method thereof |
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| CN103073587A (en) * | 2013-01-11 | 2013-05-01 | 天津师范大学 | 3-sulfonic group-4-halophenyl-3'-sulfophenyl-4''-halophenylphosphine oxide and preparation method of salt thereof |
| CN103497324A (en) * | 2013-09-29 | 2014-01-08 | 天津师范大学 | Cation-contained high-molecular polyaryl (thio) ether phosphine oxide polymers and preparation method thereof |
| CN103897179A (en) * | 2014-04-01 | 2014-07-02 | 天津师范大学 | Efficient preparation method of polymers containing phosphonic acid groups and salts |
| CN103897179B (en) * | 2014-04-01 | 2016-04-27 | 天津师范大学 | Containing the high efficiency preparation method of phosphonyl group and salt polymkeric substance thereof |
| CN104292453A (en) * | 2014-09-09 | 2015-01-21 | 天津师范大学 | Multi-sulfonated polyaromatic ether phosphine oxide high-molecular materials and preparation method and application thereof |
| CN105219060A (en) * | 2015-06-01 | 2016-01-06 | 天津师范大学 | Blend polymer containing ammonium root and sulfonate radical zwitter-ion group and preparation method thereof |
| CN105017751A (en) * | 2015-07-06 | 2015-11-04 | 天津师范大学 | Polymer blend with skeleton containing phosphonate acid and sulfonic acid group and preparation method for polymer blend |
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